Lubricating composition



to 'form a microscopic ,flim

The halogenated carbon indicated as preferable in surfaces and exertventing subsequent fusing taneo .-may be expressed as follows: ,(;1)v 1Ro Patented Sept. 9, 1941 4 UNITED STATES PATENT OFFICE .RBSSUED2,255,085 LUBRICATlNG-COMPOSITION Carl F. Prutton, Cleveland, and AlbertK. Smith,

Shaker,Heights,'0hio, assignors to The Lubri- Zol DevelopmentCorporation, Cleveland, Ohio,- a corporationofDelaware No Drawing.Application November 21, 1938,

Serial No. 241,606 4 Claims. (Cl. 252-457) October 22,1937,- now PatentNo. 2,204,620.

It has been explained that the reason why such'compounds thus improvethe extreme pressure characteristics of the lubricant probably is due tothefact that such addition agents chemically react with the bearingsurfaces under the conditions imposed by relative movement and extremepressure between the bearing surfaces t of ametallic halide whichprevents'seizing between the bearing surfaces by acting as ananti-fluxing agent.

ring compounds were is taught that the lubricating properties of a(Note: The hydrogen evolved by (2) probably would act to reduce one ormore of the organic compounds rather than to appear as free hydrogen.)

The correctness of the foregoing theory is-substantiated by the factthat when a chlorinated said patents dueto the fact that such compoundsare relatively "stable, 1'. e.,they do not readily hydrolyze in thepresence of moisture which usually occurs in varying quantities inmineral oils. In other words, the halogenated carbon ring compounds aresumciently stable so that decomposition and attack thereof upon themetallic surfaces occurs only in the areas where extreme pressure isenacountered, i. e.', on the bearing surfaces.

One theory of the action of halogen 'compounds; specifically chlorinecompounds, in increasing film strength, assumes that, as aboveindicated, under the stress of the rubbing action of bearing surfaces inmotion under load, chlorides of the bearing metals are formed on theirat HCl-ROH tact-1ra R x c main: andone of the metals of thearing'surfaces; P

an anti-fluxing effect in p reused without the addition of some otherlubri- I larly pointed out in the claims.

, ture and especially of free water is objectionable in a lubricantbesides being a highly variable factor in normal service, it isadvisable to supply an oil soluble substitute for the same.

It is the principal object of this invention, therefore, to provides.lubricating composition as the type utilizing halogenated organiccompounds as the extreme pressure addition agent but so modified as tobe effective in the manner defined without being dependent upon thepresence in-the lubricating composition of some addition material suchas water.

Other objects of our invention the description proceeds. v I

To the accomplishment of theforegoing and related ends, said invention,then consists of the means hereinafter fully described and The followingdescription sets forth d t one approved combination of ingredients em'bodying our invention, suchdisclosed means 'constituting, however, butone of various forms in which the principle of the invention may beused.

Broadly stated, thisvinvention comprises the use as a lubricant ofoxygen and halogen bearing organic compounds and more specifically,oxygen and halogen bearing organic ring compounds,

either used alone or incorporated with any suitable oil base.

The oxygen which is included inthe molecule of the addition agent actsto increase the effectiveness of the latter in raising the film strengthof a mineral. oil to which the addition agent is added or toimprove thelubricatihg properties of the halogenated compound when then cause anincrease in the film will appear particucant. The oxygen probably actsin the same way as water in making possible the formation ofhydrochloric acid as an intermediate step in the surface reaction aboveexplained.

By combining in a. single molecule the halogen and the oiwgen atoms, alubricant is afl'ectedin two ways:

First: The oxygen is always available at the exact point where required;and

Second: The molecule is more strongly ab-- sorbed by metal surfaces thansimilar halogen compounds which .do not contain oxygen.

The' latter circumstance enhances the efl'ect of equivalent to anincrease in concentration of the compound at the bearing surfaces.

We have found that certain. oxygen-containing organic ring compoundswhich havebeen chlorinated and added to a lubricatingoil are capable ofimproving the properties of such oil, particularly when employed forthin-film lubricating purposes. The addition of these certainoxygencontaining organicring compounds which have been chlorinated and addedthe lubricating oil have been found to improve the properties M thereofto an even greater extent than certain similar chlorinatedhydro-carbons, notably when added in very small amounts.

The halogen and oxygen-containing organic ring compounds added to asuitable oil base .are.

. as above indicated, preferably of the chlorinated species. andparticularly the compounds which have been found to produce verysatisfactory results, may be classified as follows; viz:

(1) Hydrogenation products of benzene (e. g. cyclohexane, cyclohexene,cyciohexadiene). (2) Hydrogenation products of naphthalene (e. g.decahydronaphcompounds containing both heterogeneous ring .small amountsof such compounds because it is 11'. Indirectly some other atom, i.e'.,- in the form of an structures and carbon ring structures.

. The foregoing compounds may also be classifled according to the natureofthe attachment of the oxygen to the compound, viz:

I. Directly attached to one or more carbon atoms, as in the case of:(1') Ethers and analogous compounds. (2") Compounds containingthe EG-OHradicle, such as alcohols and other derivatives of carbinol (includingphenols, cresols, naphthols etc.) (3) Compounds containing the carbonylC=O) radicle, such as aldehydes, ketones, organic acids, esters andsalts of organic acids, thio-acidsand esters of thio-acids. (4')Compounds in which oxygen forms a .part of the ring structure, e. g.

furan and its derivatives, anthraquinone, etc. attached through themeans of inorganic radicle, e.,g.:

- Amide Phosphate Arsenate Phosphite 'Arsenife Sulphate ChlorateSulphite Chlorite Sulphinic acid Cyanate Sulphone Hydroxylamine"Sulphonic acid Hypochlorite Sulphoxide' Nitrate Thiocyanate NitriteIsothiocyanate Nitro Thio-sulphate Nitroso 'Ihio-phosphate PerchlorateIsocyanate The halogen and oxygen-bearing organic ring compounds of theester and salt type include thalene, tetrahydronaphthalene' etc. (3)Naphthenes, naphthenic acid, etc. (0) Of mixed type such as oxygen andhalogen-bearing derivatives of indene, hydrindene, hydranthracene, etc.1 II. "Heterogeneous ring type compounds:

(a) 01' the aromatic or allied type including oxygen and halogen-bearingdeucts, or both. They may be formed by halogenarivatives of'pyridine,quinoline, etc. j

e (b) Other types such as oxygen and halo gen-bearing derivatives offurar i and its derivatives vpyrrole etc..

Included in Class II are two principal types of compounds, viz:Compounds in which all of the ring structures are of the heterogeneoustype and and of thiophene,

compounds of the aromatic type which may be classified as follows:

1. Esters and salts of an aromatic acid;

2. Esters formed by the combination of a phenol, cresol, naphthol, etc.with an organic acid of either the fatty or aromatic type;

aromatic alcohol (either mono-hydric or poly-hydric) with an organic.acid of either the fatty or aromatic type.

In addition to the substituents containing oxygen, other substituentsmay also be present with-' out'destroying, and in certain cases,improving the effect on the lubricating qualities of the 011 3..An esterformed .by the combination of an such as other aryl groups, alkylgroups, and

amino and substituted amino groups,'imin o, azo, hydrazo, hydrazine,nitrile, mercapto', sulphide,

polysulphide. Specific examples of compounds of the various classesdescribed above are halogen derivatives I of the compounds listed below.These derivatives may be substitution 'products,'addition prodtion ofthe compound listed, or of intermediate compounds or by some othermethod.

Class 'Acetanilide I(a)- -I"(3') Acetophenone I(a)-I(3') Aluminum phenylmer- I(a)'-I'(3') capto 'stearate I Aluminum phenyl I(a)-'-1'(3'lstearate 1 Amylsallcy'late I( a)I-'(2') and (3) Amino phenol In thefollowing table are given examples of aromatic acids, halogen-bearingderivatives of which may be employed as addition agents in accordancewith our invention:

I Benmic acid Benzoic acid. derivatives Azobenzoic acid Mercapto benaoicacid Lauryl benzoic acid Salicylic acid Salicylic acid derivatives Ethylsalicylic acid Carboxylic acid Carboxylic acid derivatives Pyrrolecarboxylic acid I Thiophene carboxylic acid Acetic acid "Acetic acidderivatives Class .Cinnamic acid Phenyl ethyl sulphate I(a)-II' Phthalic acid Phenyl ethyl sulphite' I(a)--II' Toluic-acid Phenyl ethylsulphone 1(a) -II' Mercapto rosolic acid Phenyl ethyl tmosul' m Amongthe esters and salts, halogen derivatives Phate of which are likewisesuitable for use as addi-. Phenyl' hydmxylamme tion agents, are theesters and salts which may Phenyl memapto gear I(a)I be derived irom'thearomatic acids listed imate mediately above and mono and *polyhydricalco- P 5g gg zgg i I(a) I hols, or other hydroxy compounds (including ca phenols). Specific examples of such alcohols and Phenyl naphthe ate1(5) (3); (3 hydroxy compounds are those specifically identi- Phenylnaphthyl keton fl under on p g 5 Phenyl mmte lf Among the salts ofaromatic acids, the halo- Phenyl oleate Ha) (3 gen-bearingderivatives ofwhich may also be em- Phenyl oxydisulphide I(a)'-I (3 loyed as additionagents, arethe salts of the Phenyl Pheml aromatic acids listedabove,includin'g the sodi- Phenyl ph gt (3) um, calcium, aluminum,magnesium, zinc and, Phenyl phenyl'naph' Kb) (3)' I'(3 A lead salts, andsalts derived from ammonia, subthenatestituted ammonias and otherorganic bases such Phenyl phenyl-stearate: I(a) I'(3') as qumdune and flm PP 9-way, Y A very important group of esters, halogenand esters abearing derivatives of which are particularly i Propyl alcohol suitedfor use as addition agents, esp cially in Phenyl steam (3 certain typesof lubricants, are the esters of alco- Phenyl t acid t 9 2 hols of thebenzenoid type. Specific examples of Pyridine steam-t9 11(5)"?! (3 suchalcohols are the following: Pyrrol stearate II(b)- I'(3) Sodiumphenylmercap- I(a)I'(3') Benz alcohol tosteamte v Phenyl ethyl alcoholSodium phenylstearate. I(a)I'(3') Benzhydml I Sodium thiobenroateI(a)I'(3')' Phenyl Stearanilid I I(a)I'(3') phenylmropyl alcoholTertiary amyl phenol 1(a) -(I) (2') Phenyl benzyl a h 'Thiobenzoic acidI(a),I'(3')' a5 mfuryl 4 Toluic acid fI(8.)-I'(3') J NaphmfienzylTricresyl phosphate -I(a)- -.II' Cinnarnyl alcohol I p yl flrsenateI(a)II' This class of esters may be derived from alco- Trlp arsenite Kn- I hols of thebenzenoid type, such as those listed p e yl Phosphate U40 above andorganic acids, either aliphatic or aro-' Triphenyl P -W imatic or from such alcohols and inorganic acids. Tri-tertiary amyl 1(a)II' 1 Examples of such organic andsinorganic acids are ph nvl phosphatethose listed under (6) (b) on page 5. Zinc benzoate. MF- The class ofunsaturated oxygen compounds is Zinc phenylstearate 1(a) I'(3)particularly suited, after halogenation or halogen treatment, for use asaddition agents in accordance with our. invention. The following is aclas- .sification or these unsaturated oxygen compounds along withspecific examples of the various groups within this sub-class; v

( 1) Unsaturated alcohols, e. g.-

Vinyl ethyl alcohol Allyl alcohol Crotonyl alcohol Oleyl alcohol vPropargyl alcohol.

(2) Unsaturated aldehydes, e.. g.

Acrolein g Crotonaldehyde Hexadienal Octatrienal Citral Propargylicaldehyde (3) Unsaturated ketones, e. g.-

, Allyl acetone Di-allyl ketone Mesityl oxide Phorone Vinyl laurylketone Acetylenic ketones (e. g.

R-CEC-CO-R'),

such as: I Allylene methyl ketone' Allylene lauryl ketohe 2,265,086 t 34ga es... Unsaturated acids, such as those Ketene listed under above.Acetyl ketene Aromatic acids, including: (4) Unsaturated ethers, e. g.Benzoic acid Di-vinyl ether 5 Phgthalic acids Di-allyl ether Salicylicacid 1 Allyl ethyl ether lfl lic acid Vinyl ethyl ether Cinnamic acidAlly1 iso-amyl ether y loliphatic acids, including: Allyl lauryl etherNaphthenic acids I Propargyl ethyl ether x ydrobenzoic acid (5)Unsaturated acids, e, g.- fieterocyclic a ids in ludin Vinyl acetic acidi i d. Vinylac'ryiic acid Pyrrol carboitylic acids Vinyl glycolic acid 5n a c 8,, n u ne:' Acrylic id Hydro-halogen acids Crotonic acidy-halogen acidsv Oleic acid ulphurous acid Linoleic acid phuric acidMaleic'acid Thiosulphuric acid ,Fumaric acid rbonic acid Linolenic acidThiocarbonic acids Elaeostearic acid y o en sulphide Propiolic acidPhosphorou a id Stearolic acid D O DhOric acids (6) Unsaturated esters,e. g. phoric acid (a) Esters of unsaturated acids. (e. g. Thiophosnhoricacids 7 those listed under (5) above aswell as cyaaic a id unsaturatedaromatic acids such as Thlocyamc acid, cinnamic and coumaric) withmono-' y flcy nic' acid and poly-hydric alcohols, or other rlc acid vhydroxy compounds (including phe-, (7) salts 0f unsaturated,acidsvincluding the-4 nols). Examples of such alcohols Ammonium andSubstituted 8 and hydroxy compounds are: m nium Methyl alcohol SodiumEthyl alcohol Aluminum Propyl alcohols Calcium Butyl alcohols MagnesiumAmyl alcohols 40 Zinc Lauryl alcohols Lead Y Cetyl alcohols Salts ofunsaturated acids general and B 810011011 more 9 6 101 such acids sthose p f yl l h listed under (5)- above and. of unsatu-Tetrahydroiurfuryl alcohol omatic acids.

Ethylene glycol Propylene glycol Di-ethylene glycol Glycerol rythritolPhenol Polyhydroxy-benzenes Alkylated phenols Naphthols Unsaturatedalcohols (e.

listed under (1) above) (1)), Esters ofunsaturated alcohols (e. g. thoselisted under '(1) above) with organic acids, either aliphatic oraromatic, or with inorganic acids.

g. those commercial 'produc Examples of such acids arealiphatic acids,including Saturated acids, such as:

Acetic acid f 'Propionic acids Butyric acids Laurie acids Palmitic' acidStearic acid Oxalic acid Citric acid Lactic acid Glycoiic acid Malonic'acid (2) Esters, produced by esteri fying the acids In addition to thecompounds listed above, tures of unsaturated oxygen-bearing or v 88-1110compounds may be used as the unsaturated reactant. Examples-oi suchmaterials are 'the'fatty oils of unsaturated character, e. g;: T

Useful Qdditional above fatty oils are, e. g.- (1) Acids, extracted fromthe oils (by direct hydr'olysis, or by saponiiicatioh and, subsequenthydrolysis, or otherwise.

(1) e. g. to formesters/analogous to any of those listed under (6) inTable No. 2.

r I ,I

ts comprising complex mix unsaturated oxygen 00211 1 pounds which may bederived from of the ('3) Soaps, produced by; saponlryin the oilsdirectly or by neutralizing the acids of (1) with alkalles, e. g. toform salts analogous to those listed under (7) in Table No. 2. Theunsaturated oxygen compounds are of particular importance and may,therefore, be I (3) Compounds containing the carbonyl C=O radicle, suchas amides, aldehydes, ketones, organic acids, esters and salts oforganic acids (including such salts of both inorganic and organic bases)thio-acids and esters and salts of thio-acids' (4) Compounds in whichoxygen-forms. a part of the ring structure, e. g. furan and itsderivatives, etc.

(55) Compounds with an inorganic radicle where the oxygen is directlyattached to a carbon atom, e. g.-

Arsenites' Thiophosphites, Hypochlorites s-hydroxylamines PhosphitesBorates Thiophosphatesn'. Indirectly attached through the means. of someother atom, i. e., in the form of an inorganic radicle, e. g.

Arsenate Phosphate Chlorate Sulphate Chlorlte Sulphite Cyanate Sulphinicacid ashydroxylamine Sulphone Nitrate 1 Sulphonic acid NitriteSulphoxide Nitro Thiophosphate Nitroso Thiophosphite OximeT'ilio-sulphate Perchlorate (Note-This class includes salts or organicbases with inorganic oxy-acids.)

In addition to the, unsaturated compounds above-described, certainunsaturated cyclic com pounds are also of use, such as thecyclo-oleflnes (e. g. cyclo-hexene) and derivatives of them.

As a matter of convenience, the halogen andoXygen-contalning-substituted diphenyls, as well as the halogenand'oxygen-containing substituted benzenes where two ormorephenyl'groups are directly linked, may be inclusively referred to ashalogen and oxygen-containing substituted polyphenyls.

This invention also contemplates the use of halogen-bearing acids (andsalts and esters derived from them) which maybe derived from compoundsformed by condensing unsaturated acids. (such as those includedamong theunsaturated oxygen-bearing compounds referred to, above) with anaromatic: compound in the presence of a catalyst such as anhydrousaluminum chloride. Italso contemplates the use of such halogen-bearingsalts and. esters as may be derived from compounds formed by similarlycondensing unsaturated salts and 'esters (such as those included amongtheunsaturated oitygeilbearing compounds referred to above) with anaromatic compound.

Examples of other halogen-bearing aromatic ,5 acids, esters and salts ofthe type contemplated ,hereby (for example those which may be derivedfrom compounds formed by condensing an aromatic acid, ester, or salt,with an unsaturated aliphatic compound) will be found in the com pendingapplication of Carl F. Prutton, Ser. No.

216,153, filed June 27, 1938. v

As previously indicated, the foregoing so-called addition agents may,for most uses, be added in minor amounts to other lubricants such asmineral oil, fish oil, lard oil, castor oil, rape-seed oil, etc., and-insome cases, depending upon the character of use, as well as thecharacter of the selected agents, the latter may be effectively used intheir pure state.

The optimum amount of the halogen compound to be employed is usuallydependent upon various considerations such as its cost, the'character ofthe selected compounds, the character of the addition agent to which thesame is added and more particularly, the character of the use to whichthe same is put. For most uses, since the cost of such halogen compoundsis usually con- 'siderably greater than lubricants such as mineral oil,optimum results are obtained by using minimum quantities to thesehalogenated addition agents. For the purpose of lubricating and reducingthe friction between relatively moving parts of an internal combustionengine such as crank case bearings, piston and cylinder surfaces,

5 as well as piston rings and valves,a composition according to ourinvention comprises a major proportion of a suitable 011 base such asmineral oil and concentrations of from one-fourth of 1% to 2% of halogencompounds of the above de- 40 fined type. If the valve structure of theengine is to be lubricated separately from the remainder of themechanism by means acting inan auxiliary fashion such as by the additionof'the lubricating-composition to the engine fuel, the composition forsuch purposes will preferably contain a largeramount of such halogencompounds,

i.'e. from about 2% to about 10%.

Whenlubricating bearing surfaces such as gears and the like whereextreme temperatures are usually not encountered a compositioncomprising a major proportion of a suitable oil base and a total of lessthan about 20% of at least one halogen and oxygen-containing organiccompound of the enumerated class will be found very satisfactory. Y Whencombined with a lubricating oil such as mineral oil, the optimum amountof the'halogen compound to be employed will depend largely upon thehalogen content of the particular com pound, its physicalcharacteristics and especially its efl'ecton the viscosity of the oil towhich it is added. when addition agents of the above enumeratedclasshaving very low viscosity are employed, and added to lubricants such asmineral oil, the limit of the amount of such compounds which may beadded and which will produceimproved results depends in a large measureupon the reduction in viscosity of the composition caused by theaddition of such compounds. When, however, the more viscous compoundsare employed, or where the particular use does not require thick filmlubrication, the so-called ad tion agents may, as previously indicated,be e ployed in their pure state.

Experiments have shown that when compounds which readily hydrolize, suchas chlorinated open chain compounds, are added to the oily base,

hydrolysis will take place to such an extent that the metal parts of anymachine being lubricated will be seriously attacked and corroded by theacid generated. 0n the other hand, the addition of chlorinated organicring compounds of we have listed a large number of classes and specificexamples of addition agents, the halogenbearin g derivatives of whichare contemplated A i. e., the unhalogenatedmaterials named, as well theabove enumerated class does not cause corrosion.

Certain of the halogen and oxygen-bearing open chain or aliphaticcompounds, in their pure state, or when added to a suitable basa doresult, however, in a lubricant particularly suitable for certainpurposes. Examples of the foregoing are halogenated fatty oils such aschlorinated cottonseed oil and chlorinated cocoanut oil. As aboveindicated, such compounds readily hydrolize and while thus not preferredas a lubricant for use in the crank case of internal combustiontengines,are nevertheless, admirably suited" for use as lubricants in metalworking such as drawing; extruding, rolling, etc., where the lubricantis in contact with the metallic surface for only relatively a shortlength of time and where 'the very slight amount of corrosion which mayresult is not particularly objectionable. Furthermore, such compoundsare admirably suited for use in lubricants in die drawing or similarlyworkingcertain corrosion resistance materials such as stainless steeland the like.

With regard to the stability of the organic ring compounds contemplated,the most resistant to hydrolysis of the halogen are those in which thehalogen is directly attached to an atom which is part of a benzenoidring structure,- Examples of such ring structures are aryl groups suchas the phenyl and naphthyl groups. In any case, for most uses, it ispreferred to have the halogen attached to an atom which is part of anorganic ring structure and especially a six-member-ed organic ringstructure.

The compositionscomprising our invention have certain advantages whenused as a lubricant of which the following may be mentioned:'

second-The friction between the bearing surfaces is reduced, especiallyin the higher pres- --sure range, belowtthat obtained with ordinarylubricants.

.Irrthe. foregoing description of,our invention an aromatic acid.

I as the halogen-free analogs of the halogenated or halogen-bearingmaterials named, may be employed to advantage in lubricatingcompositions since many of such possess valuable properties as additionagents.

These unhalogenated materials may be used, as

the sole addition agent to impart improved lubrieating properties to amineral oil (or other lubricating medium) or may advantageously be usedin conjunction with other addition agents, such as organic halogencompounds, organic phosphorus compounds (e. 'g. esters of phosphoric andphosphorous acids), organic sulphur compounds, soaps, oiliness agents,oxidation inhibitors, viscosity index improvers, 'or such other additionagents as may be employed for the same or other purposes.

Other modes of applying the" principle of our invention may be employedinstead of the one explained, change being made as regards the materialsemployed, provided the ingredients stated by anyof the following claimsor'the equivalent of such stated ingredients be employed.

- We, therefore, particularly point out and distinctly claim as ourinvention:

1. A lubricating composition comprising a major proportion of minerallubricating oil and a minor proportion of a halogen and oxygenbearingcompound of the class consisting of halogen-bearing aromatic acids,halogen-bearing esters of aromatic acids and halogen-bearing salts ofaromatic acids.

2. A lubricating composition as defined by claim 1 and being furthercharacterized by the fact that the major portion of the halogen presentis attached to a benzenoid ring structure.

3. A lubricating composition comprising "a major proportion of minerallubricating oil and a minor proportion of a halogenbearing ester of CARLF. PRU'ITON.J ALBERT K. SMITH.

